Dispersions



Patented Oct. 3, 1939 PATENT OFFICE DISPERSIONS Herbert A. Winkelmann,Chicago, Ill., assignor to Marbon Corporation, Chicago, 111., acorporation of Delaware No Drawing. Application September 2a, 1936.

- Serial No. 102,890

5 Claims.

This invention relates to an improvement in or modification of theprocess which I have described in my copending application Ser. No.20,894, filed May 10, 1935, of which the present 5 application is acontinuation in part.

' In that application Ser. No. 20,894, I have described the milling intorubber of various materials, the reaction of the composition withhydrogen chloride, and the dispersing of the composition in solvents.

The dispersion of crystalline substantially saturated rubberhydrochloride in solvents is no easy matter. This is particularly trueof those crystalline rubber hydrochlorides made by reacting solid rubberwith gaseous hydrogen chloride at elevated temperatures.

I have found that certain materials, some of which are disclosed in mycopending application, will greatly increase the ease of dispersion ofthese crystalline rubber hydrochiorides in solvents such as benzol,toluol, xylol, ethylene dichloride and the like.

In general, materials which will themselves readily dissolve in solventssuch as the above are suitable provided that they either do not reactwith hydrogen chloride or react to form products which are also readilysoluble. The materials are milled into the rubber, and the compositionreacted with gaseous hydrogen chloride under superatmospheri pressure.The resulting composition is an intimate mixture of substantiallysaturated rubber hydrochloride and the added ingredient. This intimatemixture will dissolve in mutual hot solvents with an ease far out ofproportion to what might beexpected.

For example:--thin sheet rubber 01' .02" thickness containing noadditional ingredient reacts with gaseous hydrogen chloride at 300 lbs.pressure at about 100 C. to give a substantially saturated rubberhydrochloride which on extraction with boiling benzol for one hourleaves about 20% of unextracted matter. Thin sheet rubber of .02"thickness containing 20% abietate ester gum reacted under the samecondisubstantially no residue.

' Other materials which when milled into rubber and reacted with gaseoushydrogen chloride will give similar results to glyceryl abietate are,

glyceryl maleates and other ester gums, rosin, opal wax, petroleum oils,naphthalene, parafiin wax, paraflin oils, stearic acid, pine tar,coconut oil, ester gum, modified alkyds, chlorinated diphenyls,chlorinated parafiln, chlorinated naph- 55 thalene, polycumarone andpolyindene's. I prefer of glyceryl tions and extracted in the samemanner leaves to use compatible resin gums such as rosinand glycerylabietate.

My invention is particularly applicable to making films fromsubstantially saturated crystalline rubber hydrochlorides, particularlythe crystal- 5 line rubberhydrochloride made by reacting solid sheetrubber with gaseous hydrogen chloride. These films are characterized bytheir high softening point, a property which makes them of value forlaminating purposes, where the com- 10 posite product may be used atabove room tem-- peratures. The films are also highly resistant to coldsolvents, water, gasoline and turpentine.

The following example will illustrated my invention:

Glyceryl abietate ester gum, 20 parts by weight, is milled into 100parts of uncured rubber and the composition sheeted into sheets of about.02 thickness. The sheets are reacted with gaseous hydrogen chloride at300 lbs. per sq. in. pressure 20 at 100 C. until the rubber issubstantially saturated with hydrogen chloride. The resulting mass isthen an intimate mixture of crystalline rubber hydrochloride andglyceryl abietate. An 8% solution of this compositionis then prepared 25by agitating it in boiling ethylene dichloride. A film is cast and driedat 70 C. for one-half hour.

The films were highly resistant to water, alcohol, gasoline andturpentine, and only slightly softened by cold benzol and ethylenedichloride. 30 The softening point of the ,films was markedly higherthan that of 'amorphous rubber hydrochloride.

It is to be understood that the above example is merely illustrative andnot restrictive since the 35 ingredients and proportions may be variedwithout departing from the spirit of my invention. While I prefer thatthe resin or other relatively soluble material be present in minorproportions compared to the rubber hydrochloride, this is not 40essential. Moreover, themethod ofincorporating the relatively solublematerial with the rubber hydrochloride may vary. However, I have foundthat the milling and fiuxing of the rubber with the relatively solublematerial gives superior results, particularly when the relativelysoluble material is a resin gum" I claim:

1. The improvement in the method of making dispersions of rubberhydrochloride in benzol, toluene, xylol, ethylene dichloride and thelike, which comprises fluxing rubber with a resin which is soluble inone of said solvents, until an intimate mixture of rubber and resin isobtained, calendering the mixture into thin sheets, reactwhich comprisesmilling rubber with a relatively non-volatile substance which is solublein one oi said solvents and selected from the group consisting oi.rosin, ester gums, chlorinated diphenyls, polycumarones, polyindenes,alkyd resins, paraflin wax, petroleum oils, naphthalene, stearic acid,pine tar, and cocoanut oil until an intimate mixture of rubber andobtained, calendering the mixture into thin sheets, reacting said sheetswith hydrogen chloride in the absence of solvents for said solublesubstance and the rubber whereby there is obtained an intimate mixtureof the rubber hydrochloride and said soluble substance, and agitatirigthe mixture of rubber lwdrochlorlde and said soluble substance in asolvent for said substance selected from the class of benzol, itshomologs, and ethylene dichloride.

3. The improvement in the method of making dispersions of rubberhydrochloride in benzol, toluene, xylol, ethylene dichloride and thelike, which comprises fluxing rubber with an ester gum which is solublein one or said solvents until an intimate mixture of rubber and estergum is obtained, calendering the mixture into thin sheets, reacting saidsheets with hydrogen chloride in the absence of solyents for the estergum and the the soluble substance is dichloride.

rubber whereby there is obtained an intimate mixture of rubberhydrochloride and ester gum,

-which comprises fluxing rubber with rosin until an intimate mixture ofrubber and rosin is obtained, calendering the mixture into thin sheets,

reacting said sheets with hydrogen chloride in the absence of solventsfor the rosin and the rubber whereby there is obtained an intimatemixture of rubber hydrochloride and rosin, and agitating the mixture ofrubber hydrochloride and rosin in a solvent for the rosin selected fromthe class or benzol, its homologs, and ethylene 5. The improvementgn themethod of makin dispersions of rubber hydrochloride in benzol, toluene,xylol, ethylene dichloride and the like, which comprises fluxing rubberwith a cumarone resin until an intimate mixture of rubber and cumaroneresin is obtained, calendering the mixture into thin sheets, reactingsaid sheets with hydrogen chloride in the absence of solvents for thecumarone resin and the rubber whereby there is obtained an intimatemixture of rubber hydrochloride and cumarone resin, and agitating themixture of rubber hydrochloride and cumarone resin in a solvent for thecumarone resin selected from the class of benzol, its homologs, andethylene dichloride.

HERBERT A. WINKELMANN.

